Process for regenerating a coked catalytic cracking catalyst

ABSTRACT

A process for regenerating a coked catalytic cracking catalyst which the carbon-containing deposits on the catalyst contains at least 1 wt % bio-carbon, based on the total weight of carbon present in the carbon-containing deposits is provided. Such coked catalytic cracking catalyst is contacted with an oxygen containing gas at a temperature of equal to or more than 550° C. in a regenerator to produce a regenerated catalytic cracking catalyst, heat and carbon dioxide.

This application is a divisional application of U.S. patent applicationSer. No. 13/453,835, filed Apr. 23, 2012, now U.S. Pat. No. 8,927,794which claims the benefit of European Patent Application No. 11163462.2,filed Apr. 21, 2011 the entire disclosure of which is herebyincorporated by reference.

FIELD OF THE INVENTION

The invention relates to processes for regenerating a coked catalyticcracking catalyst and catalytic cracking processes wherein a cokedcatalytic cracking catalyst is regenerated.

BACKGROUND TO THE INVENTION

The processing of petroleum oils in refineries is one or the majorsources of industrial greenhouse gas emissions. One of the mainindustrial greenhouse gases is carbon dioxide. Under the Kyoto protocol,the emission of greenhouse gases such as carbon dioxide (CO₂) has beencapped for developed countries. As a consequence many of these developedcountries have in turn capped, or have made plans to cap in the future,the emission of greenhouse gases such as carbon dioxide by industry intheir country. This has created a lively discussion how to reduce fossilCO₂ emission.

It is known that carbon is present in the atmosphere as CO₂ and thatphotoautotrophs like plants, algae and some bacteria fix this inorganiccarbon to organic carbon (carbohydrates) using sunlight for energy. Overgeological time frames (>10⁶ years) organic matter (plant materials) isfossilized to provide petroleum, natural gas and coal. When consumingthese fossil resources to make polymers, chemicals & fuel the carbon isreleased back into the atmosphere as CO₂ in a short time frame of 1-10years. The rate at which biomass is converted to fossil resources is intotal imbalance with the rate at which fossil resources are consumed andliberated. However, when using annually renewable crops or biomass asthe feedstocks for manufacturing our carbon based polymers, chemicalsand fuels, the rate at which CO₂ is fixed equals the rate at which it isconsumed and liberated. Using annually renewable carbon feedstocksallows for sustainable development of carbon based polymer materials andcontrol and even reduction of CO₂ emissions to help meet global CO₂emissions standards under the Kyoto protocol.

It would be an advancement in the art to provide processes that may helpto create sustainable CO₂ emissions or even reduce CO₂ emissions from arefinery and/or to provide processes that can be beneficial in a CO₂capture and trade scheme.

WO2010/135734 describes a method for catalytically cracking a biomassfeedstock and a refinery feedstock in a refinery unit having a fluidizedreactor. The refinery unit may include a fluidized reactor; a firstsystem providing a biomass feedstock and a refinery feedstock to thefluidized reactor and a second system for at least one of refreshing andregenerating a catalyst for the fluidized reactor. In one of theembodiments of WO2010/135734 the biomass feedstock comprises a pluralityof solid biomass particles having an average size between 50 and 1000microns. WO2010/135734 does not provide any details on the catalyst tobe regenerated and the regeneration process. In addition WO2010/135734does not describe how to improve sustainable CO₂ emissions or reducefossil CO₂ emissions from the regenerator.

SUMMARY OF THE INVENTION

Accordingly, in one embodiment provides a process for regenerating acoked catalytic cracking catalyst, comprising contacting the cokedcatalytic cracking catalyst with an oxygen containing gas at atemperature of equal to or more than 550° C. in a regenerator to producea regenerated catalytic cracking catalyst, heat and carbon dioxide,wherein the coked catalytic cracking catalyst comprisescarbon-containing deposits, which carbon-containing deposits comprise atleast 1 wt % bio-carbon, based on the total weight of carbon present inthe carbon-containing deposits.

The above process may form part of a catalytic cracking process.

Hence, in another embodiment provides a catalytic cracking processcomprising

(a) contacting a biomass material, and optionally a fluid hydrocarbonfeed, with a catalytic cracking catalyst at a temperature of more than400° C. in a catalytic cracking reactor to produce at least one crackedproduct and a coked catalytic cracking catalyst;

(b) contacting the coked catalytic cracking catalyst with an oxygencontaining gas in a regenerator to produce a regenerated catalyticcracking catalyst, heat and CO₂.

In a further embodiment provides a catalytic cracking process comprising

(a) contacting a biomass material, and optionally a fluid hydrocarbonfeed, with a catalytic cracking catalyst at a temperature of more than400° C. in a catalytic cracking reactor to produce at least one crackedproduct and a coked catalytic cracking catalyst;

(b) contacting the coked catalytic cracking catalyst with an oxygencontaining gas in a regenerator to produce a regenerated catalyticcracking catalyst, heat and CO₂; wherein the total feed of the biomassmaterial and any optional fluid hydrocarbon feed has a bio-carbon weightpercentage B1, based on the total weight of carbon in the total feed,and the coked catalytic cracking catalyst comprises carbon-containingdeposits having a bio-carbon weight percentage B2, based on the totalweight of carbon in the carbon-containing deposits; and the bio-carbonweight percentage B2 is higher than the bio-carbon weight percentage B1.

The processes advantageously allows part of the fossil CO₂ produced inthe regenerator of a catalytic cracking unit to be replaced bysustainable or so-called “green” CO₂, thereby reducing the totalemission of fossil CO₂ produced in a refinery, as explained above.

In addition, the bio-carbon on the coked catalytic cracking catalyst isa source for generating sustainable or “green” heat in the regenerator.This “green” heat can be used to make pressurized steam, for examplehigh pressure steam and/or medium pressure steam. Thereby furtherreducing the total emission of fossil CO₂ from the refinery.

Further in an embodiment provides a coked catalytic cracking catalystcomprising carbon-containing deposits, which carbon-containing depositscomprise at least 1 wt % bio-carbon, based on the total weight of carbonpresent in the carbon-containing deposits.

DETAILED DESCRIPTION OF THE INVENTION

It has been found that in a refinery, a regenerator in a catalyticcracking unit (CCU), that is used to combust coke from coked catalyticcracking catalyst, is one of the major contributors to the emission ofCO₂ by a refinery. A well known example of such a CCU is a fluidizedcatalytic cracking unit (FCCU). It has further been found that theemission of the CO₂ by a regenerator in a catalytic cracking unit (CCU)or fluidized catalytic cracking unit (FCCU) can be made more sustainableby increasing the bio-carbon content in the coke to be combusted,thereby reducing the percentage emission of fossil CO₂. In addition,total emissions may be reduced.

By processes for reducing fossil CO₂ emission is herein preferablyunderstood processes that reduce the total weight of fossil CO₂emissions from a refinery or refinery unit. As explained herein below,the present invention preferably reduces the total weight of fossil CO₂emission by replacing at least part of fossil CO₂ emission by emissionof CO₂ derived from a biomass material.

By fossil CO₂ is herein understood CO₂ derived from petroleum, naturalgas or coal. Such fossil CO₂ also includes, for example, CO₂ indirectlyderived from petroleum, natural gas or coal, such as CO₂ derived fromsynthetic (Fisher-Tropsch)crudes and/or tar-sands.

By a coked catalytic cracking catalyst is herein understood a catalyticcracking catalyst comprising carbon-containing deposits. Thecarbon-containing deposits on the catalytic cracking catalyst aresometimes also referred to as coke.

The carbon-containing deposits can be deposited on the catalyticcracking catalyst during a catalytic cracking process. Suitablecatalytic cracking processes will be explained in more detail below.

The coked catalytic cracking catalyst comprises carbon-containingdeposits, which carbon-containing deposits comprise at least 1 wt %bio-carbon, based on the total weight of carbon present in thecarbon-containing deposits.

Preferably the coked catalytic cracking catalyst comprises equal to ormore than 0.5 wt % of carbon-containing deposits, more preferably equalto or more than 1.5 wt % carbon-containing deposits, even morepreferably equal to or more than 2.5 wt % carbon-containing deposits,based on the total weight of coked catalytic cracking catalyst. Forpractical purposes the coked catalytic cracking catalyst preferablycomprises equal to or less than 30 wt % carbon-containing deposits, morepreferably equal to or less than 10 wt % carbon-containing deposits,still more preferably equal to or less than 5 wt % carbon-containingdeposits, based on the total weight of coked catalytic crackingcatalyst.

The carbon-containing deposits contain carbon atoms and can in additioncontain other elements such as for example hydrogen, sulfur and/ornitrogen. Preferably the carbon-containing deposits contain equal to ormore than 90 wt % carbon, more preferably equal to or more than 91 wt %carbon, and still more preferably equal to or more than 94 wt % carbonand preferably equal to or less than 100 wt % carbon, more preferablyequal to or less than 98 wt % carbon, based on the total weight ofcarbon-containing deposits.

For practical purposes the carbon content in the carbon-containingdeposits can be determined with a LECO analyzer TGA 701 for determiningmoisture, volatile matter, ash and fixed carbon in coke. Fixed carbon isa calculated value of the difference between 100 and the sum of themoisture, ash and volatile matter, where all values are on the samemoisture reference base.

In addition, the carbon-containing deposits may contain equal to or morethan 2 wt % elemental hydrogen, more preferably equal to or more than 6wt % elemental hydrogen and preferably equal to or less than 10 wt %elemental hydrogen, more preferably equal to or less than 8 wt %elemental hydrogen, based on the total weight of carbon-containingdeposits.

Preferably the coked catalytic cracking catalyst comprises equal to ormore than 5 wt %, more preferably equal to or more than 6 wt %, evenmore preferably equal to or more than 10 wt %, still even morepreferably equal to or more than 15 wt % of bio-carbon and preferablyequal to or less than 100 wt %, more preferably equal to or less than 90wt % and most preferably equal to or less than 80 wt % of bio-carbon,based on the total weight of carbon present in the carbon-containingdeposits.

When the coked catalytic cracking catalyst is produced in a catalyticcracking process wherein a, preferably solid, biomass material is usedin the feed in combination with a fluid hydrocarbon feed, the cokedcatalytic cracking catalyst for practical purposes preferably comprisesequal to or less than 25 wt % bio-carbon, based on the total weight ofcarbon present in the carbon-containing deposits.

For the purpose of this invention bio-carbon is understood to meanbiobased carbon as determined according to ASTM test D6866-10 titled“Standard Test Methods for Determining the Biobased Content of Solid,Liquid and Gaseous samples using Radiocarbon Analysis”, method B.

Further carbon or elemental carbon refer to carbon-atoms.

In another embodiment the coked catalytic cracking catalyst preferablycomprises equal to or more than 0.000000000001 wt %, more preferablyequal to or more than 0.00000000001 wt % of Carbon-14 isotope, based onthe total weight of carbon atoms comprised in the carbon-containingdeposits on catalyst.

The coked catalytic cracking catalyst can be produced by contacting abiomass material, optionally in the presence of a fluid hydrocarbonfeed, with a catalytic cracking catalyst, preferably at a temperature ofmore than 400° C., in a catalytic cracking reactor.

By a biomass material is herein understood a material obtained from arenewable source. By a renewable source is herein understood acomposition of matter of biological origin as opposed to a compositionof matter obtained or derived from petroleum, natural gas or coal.Without wishing to be bound by any kind of theory it is believed thatsuch material obtained from a renewable source may preferably containcarbon-14 isotope in an abundance of about 0.0000000001 %, based ontotal moles of carbon.

Preferably the renewable source is a composition of matter of cellulosicor lignocellulosic origin.

Any biomass material may be used in the process of the invention.Examples of suitable biomass materials include triglycerides, pyrolysisoils, liquefied biomass, solid biomass material and/or mixtures thereof.Examples of suitable triglyceride containing biomass materials includevegetable oils and animal fat. Examples of suitable vegetable oilsinclude palm oil, rapeseed oil, coconut oil, corn oil, soya oil,safflower oil, sunflower oil, linseed oil, olive oil and peanut oil.Examples of suitable animal fats include pork lard, beef fat, mutton fatand chicken fat.

Preferably, however, the biomass material is a solid biomass material.An advantage of using a solid biomass material as a biomass material isthat it may allow one to simplify processes, as for example operationunits for liquefaction of a biomass are not needed. More preferably thesolid biomass material is not a material used for food production.Examples of preferred solid biomass materials include aquatic plants andalgae, agricultural waste and/or forestry waste and/or paper wasteand/or plant material obtained from domestic waste.

Preferably the solid biomass material contains cellulose and/orlignocellulose. Examples of suitable cellulose- and/orlignocellulose-containing materials include agricultural wastes such ascorn stover, soybean stover, corn cobs, rice straw, rice hulls, oathulls, corn fibre, cereal straws such as wheat, barley, rye and oatstraw; grasses; forestry products and/or forestry residues such as woodand wood-related materials such as sawdust; waste paper; sugarprocessing residues such as bagasse and beet pulp; or mixtures thereof.More preferably the solid biomass material is selected from the groupconsisting of wood, sawdust, straw, grass, bagasse, corn stover and/ormixtures thereof.

Such solid biomass materials are advantageous as they do not competewith food production and are therefore considered more sustainable. Inaddition, without wishing to be bound by any kind of theory, it isbelieved that feeding of solid biomass materials into a catalyticcracking reactor results in increased coking of the catalytic crackingcatalyst with bio-carbon. It is believed that cellulosic orlignocellulosic solid biomass materials have a higher elemental ratio ofcarbon to hydrogen than triglyceride materials, such as vegetable oilsand/or animal fats, and that such higher elemental ratio of carbon tohydrogen leads to increased coking of the catalytic cracking catalyst.

The increased coking of the catalytic cracking catalyst when using solidbiomass material as a feed is advantageous in at least two ways. Firstthe increased coking causes an increased removal of carbon from thebiomass material in the feed allowing for a better hydrogen to carbonratio in the feed. Second the increased coking generates an increasedamount of sustainable or “green” heat in the regenerator, therebyincreasing the proportion of sustainable CO₂ versus fossil CO₂.

In a preferred embodiment the, preferably solid, biomass material, hasan effective molar ratio of hydrogen to carbon (H/C_(eff)) in the rangefrom equal to or more than 0 to equal to or less than 0.5. By theeffective molar ratio of hydrogen to carbon (H/C_(eff)) is understoodthe molar ratio of hydrogen to carbon after the theoretical removal ofall moles of oxygen, via water production with hydrogen originallypresent, presuming no nitrogen or sulphur present (H/C_(eff)=(H-2*O)/C).

For practical purposes the effective molar ratio of hydrogen to carbon(H/C_(eff)) can be measured as described in the article titled“Biorefineries—Synergies between Bio- and Oil Refineries for theProduction of Fuels from Biomass”, by G. W. Huber and A. Corma,published in Angewandte Chemie International Edition, 2007, volume 46,pages 7184-7201. and/or the article titled “Processing biomass-derivedoxygenates in the oil refinery: Catalytic cracking (FCC) reactionpathways and role of catalyst”, by Avelino Corma and George W. Huber,published in the Journal of Catalysis, 2007, volume 247, pages 307-327.

Any solid biomass material may have undergone drying, torrefaction,steam explosion, particle size reduction, densification and/orpelletization before being contacted with the catalyst, to allow forimproved process operability and economics.

Preferably any solid biomass material is a torrefied solid biomassmaterial. The torrefied solid biomass material can be produced bytorrefying the solid biomass material at a temperature of more than 200°C.

By torrefying or torrefaction is herein understood the treatment of thesolid biomass material at a temperature in the range from equal to ormore than 200° C. to equal to or less than 350° C. in the essentialabsence of a catalyst and in an oxygen-poor, preferably an oxygen-free,atmosphere. By an oxygen-poor atmosphere is understood an atmospherecontaining equal to or less than 15 vol. % oxygen, preferably equal toor less than 10 vol. % oxygen and more preferably equal to or less than5 vol. % oxygen. By an oxygen-free atmosphere is understood that thetorrefaction is carried out in the essential absence of oxygen.

Torrefying of the solid biomass material is preferably carried out at atemperature of more than 200° C., more preferably at a temperature equalto or more than 210° C., still more preferably at a temperature equal toor more than 220° C., yet more preferably at a temperature equal to ormore than 230° C. In addition torrefying of the solid biomass materialis preferably carried out at a temperature less than 350° C., morepreferably at a temperature equal to or less than 330° C., still morepreferably at a temperature equal to or less than 310° C., yet morepreferably at a temperature equal to or less than 300° C.

Torrefaction of the solid biomass material is preferably carried out inthe essential absence of oxygen. More preferably the torrefaction iscarried under an inert atmosphere, containing for example inert gasessuch as nitrogen, carbon dioxide and/or steam; and/or under a reducingatmosphere in the presence of a reducing gas such as hydrogen, gaseoushydrocarbons such as methane and ethane or carbon monoxide.

The torrefying step may be carried out at a wide range of pressures.Preferably, however, the torrefying step is carried out at atmosphericpressure (about 1 bar, corresponding to about 0.1 MegaPascal). Inaddition, the torrefying step may be carried out batchwise orcontinuously.

The torrefied solid biomass material has a higher energy density, ahigher mass density and greater flowability, making it easier totransport, pelletize and/or store. Being more brittle, it can be easierreduced into smaller particles.

Preferably the torrefied solid biomass material has an oxygen content inthe range from equal to or more than 10 wt %, more preferably equal toor more than 20 wt % and most preferably equal to or more than 30 wt %oxygen, to equal to or less than 60 wt %, more preferably equal to orless than 50 wt %, based on total weight of dry matter (i.e. water-freematter).

Preferably any solid biomass material is a micronized solid biomassmaterial. By a micronized solid biomass material is herein understood asolid biomass material that has a particle size distribution with a meanparticle size in the range from equal to or more than 5 micrometer toequal to or less than 5000 micrometer, as measured with a laserscattering particle size distribution analyzer. In a preferredembodiment the micronized solid biomass material is produced by reducingthe particle size of the solid biomass material, optionally before orafter such solid biomass material is torrefied. Such a particle sizereduction may for example be especially advantageous when the solidbiomass material comprises wood or torrefied wood. The particle size ofthe, optionally torrefied, solid biomass material can be reduced in anymanner known to the skilled person to be suitable for this purpose.Suitable methods for particle size reduction include crushing, grindingand/or milling. The particle size reduction may preferably be achievedby means of a ball mill, hammer mill, (knife) shredder, chipper, knifegrid, or cutter.

Preferably the solid biomass material has a particle size distributionwhere the mean particle size lies in the range from equal to or morethan 5 micrometer (micron), more preferably equal to or more than 10micrometer, even more preferably equal to or more than 20 micrometer,and most preferably equal to or more than 100 micrometer to equal to orless than 5000 micrometer, more preferably equal to or less than 1000micrometer and most preferably equal to or less than 500 micrometer.

Most preferably the solid biomass material has a particle sizedistribution where the mean particle size is equal to or more than 100micrometer to avoid blocking of pipelines and/or nozzles. Mostpreferably the solid biomass material has a particle size distributionwhere the mean particle size is equal to or less than 3000 micrometer toallow easy injection into the riser reactor.

For practical purposes the particle size distribution and mean particlesize of the solid biomass material can be determined with a LaserScattering Particle Size Distribution Analyzer, preferably a HoribaLA950, according to the ISO 13320 method titled “Particle sizeanalysis—Laser diffraction methods”.

In addition to the, preferably solid, biomass material preferably also afluid hydrocarbon feed may be contacted with the catalytic crackingcatalyst in the catalytic cracking reactor.

By a hydrocarbon feed is herein understood a feed that contains one ormore hydrocarbon compounds. By hydrocarbon compounds are hereinunderstood compounds that contain both hydrogen and carbon andpreferably consist of hydrogen and carbon. By a fluid hydrocarbon feedis herein understood a hydrocarbon feed that is not in a solid state.The fluid hydrocarbon co-feed is preferably a liquid hydrocarbonco-feed, a gaseous hydrocarbon co-feed, or a mixture thereof. The fluidhydrocarbon co-feed can be fed to a catalytic cracking reactor in anessentially liquid state, in an essentially gaseous state or in apartially liquid-partially gaseous state. When entering the catalyticcracking reactor in an essentially or partially liquid state, the fluidhydrocarbon co-feed preferably vaporizes upon entry and preferably iscontacted in the gaseous state with the catalytic cracking catalystand/or the solid biomass material.

The fluid hydrocarbon feed can be any non-solid hydrocarbon feed knownto the skilled person to be suitable as a feed for a catalytic crackingunit. The fluid hydrocarbon feed can for example be obtained from aconventional crude oil (also sometimes referred to as a petroleum oil ormineral oil), an unconventional crude oil (that is, oil produced orextracted using techniques other than the traditional oil well method)or a Fisher Tropsch oil and/or a mixture thereof.

When the biomass material is a solid biomass material, the fluidhydrocarbon feed may also be a fluid hydrocarbon feed from a renewablesource, such as for example a pyrolysis oil, a vegetable oil, liquefiedbiomass and/or mixtures thereof.

In one embodiment the fluid hydrocarbon feed is derived from a,preferably conventional, crude oil. Examples of conventional crude oilsinclude West Texas Intermediate crude oil, Brent crude oil, Dubai-Omancrude oil, Arabian Light crude oil, Midway Sunset crude oil or Tapiscrude oil.

More preferably the fluid hydrocarbon feed comprises a fraction of a,preferably conventional, crude oil or renewable oil. Preferred fluidhydrocarbon feeds include straight run (atmospheric) gas oils, flasheddistillate, vacuum gas oils (VGO), coker gas oils, diesel, gasoline,kerosene, naphtha, liquefied petroleum gases, atmospheric residue (“longresidue”) and vacuum residue (“short residue”) and/or mixtures thereof.Most preferably the fluid hydrocarbon feed comprises a long residue, avacuum gas oil and/or mixtures thereof.

The composition of the fluid hydrocarbon feed may vary widely. The fluidhydrocarbon feed may for example contain paraffins, naphthenes, olefinsand/or aromatics.

Preferably the fluid hydrocarbon feed comprises in the range from equalto or more than 50 wt %, more preferably from equal to or more than 75wt %, and most preferably from equal to or more than 90 wt % to equal toor less than 100 wt % of compounds consisting only of carbon andhydrogen, based on the total weight of the fluid hydrocarbon feed.

Preferably the fluid hydrocarbon feed comprises equal to or more than 1wt % paraffins, more preferably equal to or more than 5 wt % paraffins,and most preferably equal to or more than 10 wt % paraffins, andpreferably equal to or less than 100 wt % paraffins, more preferablyequal to or less than 90 wt % paraffins, and most preferably equal to orless than 30 wt % paraffins, based on the total fluid hydrocarbon feed.By paraffins both normal-, cyclo- and branched-paraffins are understood.

In a preferred embodiment the fluid hydrocarbon feed comprises orconsists of a paraffinic fluid hydrocarbon feed. By a paraffinic fluidhydrocarbon feed is herein understood a fluid hydrocarbon feedcomprising at least 50 wt % of paraffins, preferably at least 70 wt % ofparaffins, based on the total weight of the fluid hydrocarbon feed. Forpractical purposes the paraffin content of all fluid hydrocarbon feedshaving an initial boiling point of at least 260° C. can be measured bymeans of ASTM method D2007-03 titled “Standard test method forcharacteristic groups in rubber extender and processing oils and otherpetroleum-derived oils by clay-gel absorption chromatographic method”,wherein the amount of saturates will be representative for the paraffincontent. For all other fluid hydrocarbon feeds the paraffin content ofthe fluid hydrocarbon feed can be measured by means of comprehensivemulti-dimensional gas chromatography (GC×GC), as described in P. J.Schoenmakers, J. L. M. M. Oomen, J. Blomberg, W. Genuit, G. van Velzen,J. Chromatogr. A, 892 (2000) p. 29 and further.

Examples of paraffinic fluid hydrocarbon feeds include so-calledFischer-Tropsch derived hydrocarbon streams such as described inWO2007/090884 and herein incorporated by reference, or a hydrogen richfeed like hydrotreater product or hydrowax. By Hydrowax is understoodthe bottoms fraction of a hydrocracker. Examples of hydrocrackingprocesses which may yield a bottoms fraction that can be used as fluidhydrocarbon feed, are described in EP-A-699225, EP-A-649896,WO-A-97/18278, EP-A-705321, EP-A-994173 and U.S. Pat. No. 4,851,109 andherein incorporated by reference.

In a preferred embodiment the fluid hydrocarbon feed comprises equal toor more than 8 wt % elemental hydrogen, more preferably more than 12 wt% elemental hydrogen (i.e. hydrogen atoms), based on the total fluidhydrocarbon feed on a dry basis (i.e. water-free basis). A high contentof elemental hydrogen, such as a content of equal to or more than 8 wt%, allows the hydrocarbon feed to act as a cheap hydrogen donor in thecatalytic cracking process. A particularly preferred fluid hydrocarbonfeed having an elemental hydrogen content of equal to or more than 8 wt% is Fischer-Tropsch derived waxy raffinate. Such Fischer-Tropschderived waxy raffinate may for example comprise about 85 wt % ofelemental carbon and 15 wt % of elemental hydrogen.

Without wishing to be bound by any kind of theory it is further believedthat a lower weight ratio of fluid hydrocarbon feed to, preferablysolid, biomass material results in more bio-carbon on the cokedcatalytic cracking catalyst.

Preferably the combination of the, preferably solid, biomass materialand the fluid hydrocarbon feed has an overall molar ratio of hydrogen tocarbon (H/C) of equal to or more than 1.1 to 1 (1.1/1), more preferablyof equal to or more than 1.2 to 1 (1.2/1), most preferably of equal toor more than 1.3 to 1 (1.3/1).

In a preferred embodiment an effective molar ratio of hydrogen to carbon(H/C_(eff)) is used and the combination of the, preferably solid,biomass material and the fluid hydrocarbon feed preferably has anoverall effective molar ratio of hydrogen to carbon (H/C_(eff)) of equalto or more than 1.1 to 1 (1.1/1), more preferably of equal to or morethan 1.2 to 1 (1.2/1), most preferably of equal to or more than 1.3 to 1(1.3/1).

If a fluid hydrocarbon feed is present, the weight ratio of the biomassmaterial to fluid hydrocarbon feed may vary widely.

When the biomass material is a solid biomass material, the weight ratioof fluid hydrocarbon feed to solid biomass material is preferably equalto or more than 50 to 50 (5:5), more preferably equal to or more than 70to 30 (7:3), still more preferably equal to or more than 80 to 20 (8:2),even still more preferably equal to or more than 90 to 10 (9:1). Forpractical purposes the weight ratio of fluid hydrocarbon feed to solidbiomass material is preferably equal to or less than 99.9 to 0.1(99.9:0.1), more preferably equal to or less than 95 to 5 (95:5). Thefluid hydrocarbon feed and the solid biomass material are preferablybeing fed to the catalytic cracking reactor in a weight ratio within theabove ranges.

The amount of solid biomass material, based on the total weight of solidbiomass material and fluid hydrocarbon feed supplied to the catalyticcracking reactor, is preferably equal to or less than 30 wt %, morepreferably equal to or less than 20 wt %, most preferably equal to orless than 10 wt % and even more preferably equal to or less than 5 wt %.For practical purposes the amount of solid biomass material present,based on the total weight of solid biomass material and fluidhydrocarbon feed supplied to the riser reactor, is preferably equal toor more than 0.1 wt %, more preferably equal to or more than 1 wt %.

When the biomass material comprises a pyrolysis oil, a vegetable oil,liquefied biomass, animal fat or a mixture thereof, the feed supplied tothe catalytic cracking reactor preferably comprises in the range fromequal to or more than 5 wt %, more preferably equal to or more than 10wt % to equal to or less than 100 wt %, more preferably equal to or lessthan 90 wt % of such pyrolysis oil, a vegetable oil, animal fat or amixture thereof, based on the total weight of the feed.

The catalytic cracking reactor can be any catalytic cracking reactorknown in the art to be suitable for the purpose, including for example afluidized bed reactor or a riser reactor. Most preferably the catalyticcracking reactor is a riser reactor.

Preferably this catalytic cracking reactor is part of a catalyticcracking unit, more preferably of a fluidized catalytic cracking (FCC)unit.

In one embodiment, where the biomass material is a solid biomassmaterial, preferably a suspension of solid biomass material suspended ina fluid hydrocarbon feed is supplied to a riser reactor. Preferences forthe fluid hydrocarbon feed are as described herein above.

In another embodiment, where the biomass material is a solid biomassmaterial, the solid biomass material is supplied to the riser reactor ata location downstream of a location where a fluid hydrocarbon feed issupplied to the riser reactor. Without wishing to be bound by any kindof theory it is believed that by allowing the fluid hydrocarbon feed tocontact the catalytic cracking catalyst first, cheap hydrogen may begenerated. The availability of this cheap hydrogen may assist in thereduction of coke formation when the solid biomass material is contactedwith the catalytic cracking catalyst more downstream in the riserreactor.

In another preferred embodiment, where the biomass material is a solidbiomass material, the catalytic cracking reactor is a riser reactor andthe fluid hydrocarbon feed is supplied to the riser reactor at alocation downstream of the location where the solid biomass material issupplied to the riser reactor.

Without wishing to be bound to any kind of theory it is believed thatsupplying the solid biomass material upstream of the fluid hydrocarbonfeed leads to a higher weight percentage of bio-carbon in thecarbon-containing deposits on the coked catalytic cracking catalyst. Atthe location where the fluid hydrocarbon feed is supplied to the riserreactor, the solid biomass material may already be partly or whollyconverted into oil, coke and/or cracked products. In a preferredembodiment in the range from equal to or more than 5 wt %, morepreferably equal to or more than 10 wt % to equal to or less than 100 wt% of the solid biomass material is converted into oil, coke and/orcracked products at such a location. The cracked products formed arepreferably in the gaseous state.

In a still further embodiment, a suspension of solid biomass materialsuspended in a first fluid hydrocarbon feed is supplied to the riserreactor at a first location and a second fluid hydrocarbon feed issupplied to the riser reactor at a second location downstream of thefirst location. Preferences for the first and second fluid hydrocarbonfeed are as described herein above.

By a riser reactor is herein understood an elongated, preferablyessentially tube-shaped, reactor suitable for carrying out catalyticcracking reactions. Suitably a fluidized catalytic cracking catalystflows in the riser reactor from the upstream end to the downstream endof the reactor. The elongated, preferably essentially tube-shaped,reactor is preferably oriented in an essentially vertical manner.Preferably, the fluidized catalytic cracking catalyst flows from thebottom of the riser reactor upwards to the top of the riser reactor.

Examples of suitable riser reactors are described in the Handbook titled“Fluid Catalytic Cracking technology and operations”, by Joseph W.Wilson, published by PennWell Publishing Company (1997), chapter 3,especially pages 101 to 112, herein incorporated by reference.

The riser reactor may be a so-called internal riser reactor or aso-called external riser reactor as described therein.

Most preferably the internal riser reactor is an essentially verticalessentially tube-shaped reactor, that may have an essentially verticalupstream end located outside a vessel and an essentially verticaldownstream end located inside the vessel. The vessel is suitably areaction vessel suitable for catalytic cracking reactions and/or avessel that comprises one or more cyclone separators and/or swirl tubes.The internal riser reactor is especially advantageous when part of thefeed comprises a solid biomass material or a pyrolysis oil. The solidbiomass material may be converted into an intermediate oil product.Without wishing to be bound to any kind of theory it is believed thatthis intermediate oil product or pyrolysis oil may be more prone topolymerization than conventional oils due to oxygen-containinghydrocarbons and/or olefins that may be present in the intermediate oilproduct. In addition the intermediate oil product or pyrolysis oil maybe more corrosive than conventional oils due to oxygen-containinghydrocarbons that may be present. The use of an internal riser reactorallows one to reduce the risk of plugging due to polymerization and/orto reduce the risk of corrosion, thereby increasing safety and hardwareintegrity.

By an external riser reactor is herein preferably understood a riserreactor that is located outside a vessel. The external riser reactor cansuitably be connected via a so-called crossover to a vessel.

When an external riser reactor is used, it may be advantageous to use anexternal riser reactor with a curve or low velocity zone at itstermination as for example illustrated in the Handbook titled “FluidCatalytic Cracking technology and operations”, by Joseph W. Wilson,published by PennWell Publishing Company (1997), chapter 3, figure 3-7,herein incorporated by reference.

It has been advantageously found that a part of the catalytic crackingcatalyst may deposit in the curve or low velocity zone, thereby forminga protective layer against corrosion and/or erosion by the catalyticcracking catalyst and any residual solid particles and anyoxygen-containing hydrocarbons as explained above.

The length of the riser reactor may vary widely. For practical purposesthe riser reactor preferably has a length in the range from equal to ormore than 10 meters, more preferably equal to or more than 15 meters andmost preferably equal to or more than 20 meters, to equal to or lessthan 65 meters, more preferably equal to or less than 55 meters and mostpreferably equal to or less than 45 meters.

In a preferred embodiment the, preferably solid, biomass material issupplied to the riser reactor, at the bottom of this reactor. It may beadvantageous to also add a lift gas at the bottom of the riser reactor.Examples of such a liftgas include steam or vaporized naphtha, steam ismost preferred as a lift gas. Most preferably the liftgas consists ofsteam. If the biomass material is supplied at the bottom of the riserreactor, is may optionally be mixed with such a lift gas before entry inthe riser reactor, and fed to the reactor as a mixture of biomassmaterial and liftgas. If the biomass material is not mixed with theliftgas prior to entry into the riser reactor it may be fedsimultaneously with the liftgas (at one and the same location) to theriser reactor, and optionally mixed upon entry of the riser reactor; orit may be fed separately from any liftgas (at different locations) tothe riser reactor.

When both biomass material and steam are introduced into the bottom ofthe riser reactor, the steam-to-biomass material weight ratio ispreferably in the range from equal to or more than 0.01:1, morepreferably equal to or more than 0.05:1 to equal to or less than 5:1,more preferably equal to or less than 1.5:1.

When solid biomass material is introduced at the bottom of the riserreactor, it can be advantageous to increase the residence time of thesolid biomass material at that part of the riser reactor by increasingthe diameter of the riser reactor pipe at the bottom. Hence in apreferred embodiment the catalytic cracking comprises a riser reactorpipe having an enlarged bottom section, for example in the form of alift pot. Such a liftpot preferably has a diameter larger than thediameter of the riser reactor pipe, more preferably a diameter in therange from equal to or more than 0.4 to equal to or less than 5 meters,most preferably a diameter in the range from equal to or more than 1 toequal to or less than 2 meters. Without wishing to be bound by any kindof theory, such is believed to lead to an increased bio-carbon contentin the carbon containing deposits of the coked catalytic crackingcatalyst.

Preferably the temperature in the reactor ranges from equal to or morethan 450° C., more preferably from equal to or more than 480° C., toequal to or less than 800° C., more preferably equal to or less than750° C.

Preferably the temperature at the location where the biomass material issupplied to the catalytic cracking reactor lies in the range from equalto or more than 500° C., more preferably equal to or more than 550° C.,and most preferably equal to or more than 600° C., to equal to or lessthan 800° C., more preferably equal to or less than 750° C.

When a solid biomass material is supplied to the catalytic crackingreactor it can be advantageous to supply the solid biomass material to alocation in the catalytic cracking reactor where the temperature isslightly higher, for example where the temperature lies in the rangefrom equal to or more than 700° C., more preferably equal to or morethan 720° C., even more preferably equal to or more than 732° C. toequal to or less than 800° C., more preferably equal to or less than750° C. Without wishing to be bound by any kind of theory, such isbelieved to lead to an increased weight percentage of bio-carbon in thecarbon-containing deposits of the coked catalytic cracking catalyst.

Preferably the pressure in the catalytic cracking reactor ranges fromequal to or more than 0.5 bar absolute to equal to or less than 10 barabsolute (0.05 MegaPascal-1.0 MegaPascal), more preferably from equal toor more than 1.0 bar absolute to equal to or less than 6 bar absolute(0.1 MegaPascal to 0.6 MegaPascal).

Preferably the total average residence time of the biomass material liesin the range from equal to or more than 1 second, more preferably equalto or more than 1.5 seconds and even more preferably equal to or morethan 2 seconds to equal to or less than 10 seconds, preferably equal toor less than 5 seconds and more preferably equal to or less than 4seconds.

The weight ratio of catalyst to feed (that is the total feed of solidbiomass material and, if present, any fluid hydrocarbon feed)—hereinalso referred to as catalyst: feed ratio—preferably lies in the rangefrom equal to or more than 1:1, more preferably from equal to or morethan 2:1 and most preferably from equal to or more than 3:1 to equal toor less than 150:1, more preferably to equal to or less than 100:1, mostpreferably to equal to or less than 50:1.

The weight ratio of catalyst to biomass material (catalyst: biomassratio) at the location where the biomass material is supplied to theriser reactor preferably lies in the range from equal to or more than1:1, more preferably from equal to or more than 2:1 and most preferablyfrom equal to or more than 3:1 to equal to or less than 150:1, morepreferably to equal to or less than 100:1, most preferably to equal toor less than 50:1.

When a solid biomass material is supplied to the catalytic crackingreactor it can be advantageous to supply the solid biomass material to alocation in the catalytic cracking reactor where the weight ratio ofcatalyst to solid biomass material (catalyst: solid biomass ratio)isslightly higher, for example in the range from equal to or more than2:1, more preferably from equal to or more than 3:1 and most preferablyfrom equal to or more than 5:1 to equal to or less than 150:1, morepreferably to equal to or less than 100:1. Without wishing to be boundby any kind of theory, such is believed to lead to an increased weightpercentage of bio-carbon in the carbon-containing deposits of the cokedcatalytic cracking catalyst.

In a preferred embodiment the fluid hydrocarbon feed may be introducedto the catalytic cracking reactor at a location where the, preferablysolid, biomass material already had a residence time in the range fromequal to or more than 0.01 seconds, more preferably from equal to ormore than 0.05 seconds, and most preferably from equal to or more than0.1 seconds to equal to or less than 2 seconds, more preferably to equalto or less than 1 seconds, and most preferably to equal to or less than0.5 seconds.

In a preferred embodiment the ratio between the residence time for anysolid biomass material to the residence time for the fluid hydrocarbonfeed (residence solid biomass:residence hydrocarbon ratio) lies in therange from equal to or more than 1.01:1, more preferably from equal toor more than 1.1:1 to equal to or less than 3:1, more preferably toequal to or less than 2:1.

Preferably any solid biomass material is introduced to the riser reactorat a location with temperature T1 and the fluid hydrocarbon feed isintroduced to the riser reactor at a location with temperature T2 andtemperature T1 is higher than temperature T2. Without wishing to bebound by any kind of theory, such is believed to lead to an increasedweight percentage of bio-carbon in the carbon-containing deposits of thecoked catalytic cracking catalyst. Preferably both T1 and T2 are equalto or more than 400° C., more preferably equal to or more than 450° C.

The catalytic cracking catalyst can be any catalyst known to the skilledperson to be suitable for use in a cracking process. Preferably, thecatalytic cracking catalyst comprises a zeolitic component. In addition,the catalytic cracking catalyst can contain an amorphous binder compoundand/or a filler. Examples of the amorphous binder component includesilica, alumina, titania, zirconia and magnesium oxide, or combinationsof two or more of them. Examples of fillers include clays (such askaolin).

The zeolite is preferably a large pore zeolite. The large pore zeoliteincludes a zeolite comprising a porous, crystalline aluminosilicatestructure having a porous internal cell structure on which the majoraxis of the pores is in the range of 0.62 nanometer to 0.8 nanometer.The axes of zeolites are depicted in the ‘Atlas of Zeolite StructureTypes’, of W. M. Meier, D. H. Olson, and Ch. Baerlocher, Fourth RevisedEdition 1996, Elsevier, ISBN 0-444-10015-6. Examples of such large porezeolites include FAU or faujasite, preferably synthetic faujasite, forexample, zeolite Y or X, ultra-stable zeolite Y (USY), Rare Earthzeolite Y (=REY) and Rare Earth USY (REUSY). According to the presentinvention USY is preferably used as the large pore zeolite.

The catalytic cracking catalyst can also comprise a medium pore zeolite.The medium pore zeolite that can be used according to the presentinvention is a zeolite comprising a porous, crystalline aluminosilicatestructure having a porous internal cell structure on which the majoraxis of the pores is in the range of 0.45 nanometer to 0.62 nanometer.Examples of such medium pore zeolites are of the MFI structural type,for example, ZSM-5; the MTW type, for example, ZSM-12; the TONstructural type, for example, theta one; and the FER structural type,for example, ferrierite. According to the present invention, ZSM-5 ispreferably used as the medium pore zeolite.

According to another embodiment, a blend of large pore and medium porezeolites may be used. The ratio of the large pore zeolite to the mediumpore size zeolite in the cracking catalyst is preferably in the range of99:1 to 70:30, more preferably in the range of 98:2 to 85:15.

The total amount of the large pore size zeolite and/or medium porezeolite that is present in the cracking catalyst is preferably in therange of 5 wt % to 40 wt %, more preferably in the range of 10 wt % to30 wt %, and even more preferably in the range of 10 wt % to 25 wt %relative to the total mass of the catalytic cracking catalyst.

Preferably the catalytic cracking catalyst is contacted in a cocurrentflow configuration with a cocurrent flow of the, preferably solid,biomass material and optionally fluid hydrocarbon feed.

The coked catalytic cracking catalyst produced can be regenerated withthe process for regeneration according to the invention.

By contacting the coked catalytic cracking catalyst with an oxygencontaining gas in a regenerator at a temperature of equal to or morethan 550° C., the carbon-containing deposits, that can be deposited onthe catalyst as a result of the catalytic cracking reaction, are burnedoff to restore the catalyst activity.

During the regeneration of the coked catalytic cracking catalyst, carbondioxide (CO₂) and optionally carbon monoxide (CO) and/or nitrogen oxides(NOx) and/or sulphur oxides (SOx) is produced.

The oxygen containing gas may be any oxygen containing gas known to theskilled person to be suitable for use in a regenerator. For example theoxygen containing gas may be air or oxygen-enriched air. By oxygenenriched air is herein understood air comprising more than 21 vol. %oxygen (O₂), more preferably air comprising equal to or more than 22vol. % oxygen, based on the total volume of air.

In one preferred embodiment the oxygen containing gas comprises equal toor more than 21 vol. % oxygen, more preferably equal to or more than 22vol. % oxygen, and most preferably equal to or more than 25 vol. %oxygen, based on the total volume of the oxygen-containing gas. Forpractical purposes the oxygen containing gas may preferably compriseequal to or less than 100 vol. % oxygen, more preferably equal to orless than 50 vol. % oxygen, even more preferably equal to or less than30 vol. % oxygen, based on the total volume of the oxygen-containinggas.

The use of oxygen-enriched gas, and preferably oxygen-enriched air, isadvantageous on its own and therefore the current invention furtherprovides a catalytic cracking process comprising contacting a,preferably solid, biomass material, and optionally a fluid hydrocarbonfeed, with a catalytic cracking catalyst at a temperature of more than400° C. in a catalytic cracking reactor to produce one or more crackedproducts and a coked catalytic cracking catalyst; contacting the cokedcatalytic cracking catalyst with an oxygen containing gas in aregenerator to produce a regenerated catalytic cracking catalyst, heatand CO₂; wherein the oxygen containing gas comprises more than 21 vol. %oxygen, based on the total volume of oxygen-containing gas.

Preferences for such a process using oxygen-enriched gas are asdescribed herein above and further herein below.

The use of an oxygen-enriched gas, preferably oxygen-enriched air, isespecially advantageous when using a biomass material, preferably asolid biomass material, in the feed. Without wishing to be bound by anykind of theory it is believed that the use of especially a solid biomassmaterial in the feed may lead to additional bio-carbon in thecarbon-containing deposits on the catalytic cracking catalyst. Whenusing oxygen-enriched gas more bio-carbon can be burned off toadvantageously create more “green” heat, thereby reducing fossil CO₂elsewhere in a refinery.

Preferably the coked catalytic cracking catalyst is contacted with theoxygen-containing gas in the regenerator at a temperature in the rangefrom equal to or more than 575° C., more preferably from equal to ormore than 600° C., even more preferably from equal to or more than 650°C., to equal to or less than 950° C., more preferably to equal to orless than 850° C.

In an especially preferred embodiment the coked catalytic crackingcatalyst is regenerated at a temperature of equal to or more than 700°C., more preferably equal to or more than 720° C., most preferably equalto or more than 732° C. Regenerating the coked catalytic crackingcatalyst at a temperature of equal to or more than 700° C.advantageously allows one to ensure that all coke, including anyadditional coke due to the use of for example a solid biomass materialin the feed, is burned off.

This advantageously creates more “green” heat.

In addition it allows one to feed regenerated catalytic crackingcatalyst having a temperature of equal to or more than 700° C., morepreferably equal to or more than 720° C., most preferably equal to ormore than 732° C., to a catalytic cracking reactor. This is especiallyadvantageous when a riser reactor is used, where solid biomass materialis supplied to the riser reactor more upstream of the fluid hydrocarbonfeed. A catalytic cracking catalyst having a temperature of equal to ormore than 700° C. advantageously allows one to convert a majority of thesolid biomass material before this is contacted with the fluidhydrocarbon feed.

Alternatively or in addition the excess of heat produced when operatingthe regenerator at a temperature of equal to or more than 700° C. mayconveniently be used to heat water and/or generate medium pressuresteam, high pressure steam and/or even very high pressure steam. Bymedium pressure steam is herein understood steam at a pressure in therange from 10 to 30 bar gauge (0.9 to 2.9 MegaPascal). By high pressuresteam is herein understood steam at a pressure in the range from 30 to70 bar gauge (2.9 to 6.9 MegaPascal). By very high pressure steam isherein understood steam at a pressure in the range from 70 to 100 bargauge (6.9 to 9.9 MegaPascal). The steam will preferably be superheatedsteam to avoid condensation thereof at the specified pressure. Suchmedium pressure steam, high pressure steam and/or very high pressuresteam can conveniently be used elsewhere in the refinery, for example aslift gas for the catalytic cracking reactor.

Preferably the coked catalytic cracking catalyst is regenerated at apressure in the range from equal to or more than 0.5 bar absolute toequal to or less than 10 bar absolute (0.05 MegaPascal to 1.0MegaPascal), more preferably from equal to or more than 1.0 bar absoluteto equal to or less than 6 bar absolute (0.1 MegaPascal to 0.6MegaPascal).

The regenerator may have any design known by the person skilled in theart to be suitable for regeneration of a coked catalytic crackingcatalyst. For example the regenerator may be designed as described inthe Handbook titled “Fluid Catalytic Cracking technology andoperations”, by Joseph W. Wilson, published by PennWell PublishingCompany (1997), chapter 4, especially pages 131 to 155, hereinincorporated by reference.

The regenerator may comprise one stage or, if desired, two or morestages.

Preferably the regenerator comprises a dense phase catalyst bed toppedby a dilute phase catalyst bed and preferably one or more cyclones tocollect entrained catalyst particles and return them to the dense phase.

In addition the regenerator may contain one or more catalyst coolers,preferably so-called dense phase catalyst coolers such as for exampledepicted in figures 4-17, 4-18a and 4-18b of the above Handbook byJoseph W. Wilson. These dense phase catalyst coolers comprise one ormore bayonet shaped tubes arranged in one or more rings in theregenerator. The catalytic cracking catalyst is preferably fluidized bythe oxygen-containing gas and flows on the shell side of the cooler.Water is fed into the bayonet shaped tubes and at least partly convertedinto steam.

The use of regenerators comprising one or more catalyst coolers isespecially preferred when a solid biomass material is used in the feed,causing additional coking of the catalytic cracking catalyst. Inaddition the use of regenerators comprising one or more catalyst coolersis especially preferred when operating the regenerator at a temperatureof equal to or more than 700° C.

During regeneration of the coked catalytic cracking catalyst, aregenerated catalytic cracking catalyst, carbon dioxide and heat areproduced.

The heat generated in the exothermic regeneration is preferably employedto provide energy for an endothermic catalytic cracking step. In apreferred embodiment, the process according to the inventionadvantageously allows for a sufficient amount of coke deposited on thecatalytic cracking catalyst such that the endothermic catalytic crackingstep can be carried out without supplying additional heat.

In addition part of the heat generated in the exothermic regenerationstep may be employed to heat water and/or produce for example mediumpressure steam, high pressure steam and/or very high pressure steam asdescribed herein above.

Catalytic cracking of a biomass material with a catalytic crackingcatalyst to produce a coked catalytic cracking catalyst and regenerationof the coked catalytic cracking catalyst as described herein ispreferably carried out in a catalytic cracking unit. This catalyticcracking unit preferably comprises at least a catalytic cracking reactorand a regenerator as described herein above.

In a preferred embodiment the coked catalytic cracking catalyst isproduced in a catalytic cracking process comprising:

a catalytic cracking step comprising contacting the, preferably solid,biomass material and optionally a fluid hydrocarbon feed with thecatalytic cracking catalyst at a temperature of more than 400° C. in acatalytic cracking reactor and catalytically cracking the solid, biomassmaterial and optional fluid hydrocarbon feed to produce one or morecracked products and a coked catalytic cracking catalyst;

a separation step comprising separating the one or more cracked productsfrom the coked catalytic cracking catalyst;

a regeneration step comprising regenerating coked catalytic crackingcatalyst to produce a regenerated catalytic cracking catalyst, heat andcarbon dioxide; and a recycle step comprising recycling the regeneratedcatalytic cracking catalyst to the catalytic cracking step.

In such a process the total feed of the biomass material and any fluidhydrocarbon feed preferably has a bio-carbon weight percentage B1, basedon the total weight of carbon in the total feed, and the coked catalyticcracking catalyst preferably comprises carbon-containing deposits havinga bio-carbon weight percentage B2, based on the total weight of carbonin the carbon-containing deposits; and the bio-carbon weight percentageB2 is preferably higher than the bio-carbon weight percentage B1.

The catalytic cracking step is preferably carried out as describedherein before.

The separation step is preferably carried out with the help of one ormore cyclone separators and/or one or more swirl tubes. Suitable ways ofcarrying out the separation step are for example described in theHandbook titled “Fluid Catalytic Cracking; Design, Operation, andTroubleshooting of FCC Facilities” by Reza Sadeghbeigi, published byGulf Publishing Company, Houston Tex. (1995), especially pages 219-223.The cyclone separators are preferably operated at a velocity in therange from 18 to 80 meters/second, more preferably at a velocity in therange from 25 to 55 meters/second.

In addition the separation step may further comprise a stripping step.In such a stripping step the coked catalyst may be stripped to recoverthe products absorbed on the coked catalyst before the regenerationstep. These products may be recycled and added to the cracked productstream obtained from the catalytic cracking step.

The regeneration step preferably comprises contacting of the cokedcatalytic cracking catalyst with an oxygen containing gas in aregenerator as described herein before.

The regenerated catalytic cracking catalyst can be recycled to thecatalytic cracking step. In a preferred embodiment a side stream ofmake-up catalyst is added to the recycle stream to make-up for loss ofcatalyst in the reaction zone and regenerator.

When catalytically cracking the biomass material and optionally thefluid hydrocarbon feed one or more cracked products are produced. In apreferred embodiment this/these one or more cracked products is/aresubsequently fractionated to produce one or more product fractions.

The one or more cracked products may contain one or moreoxygen-containing-hydrocarbons. Examples of suchoxygen-containing-hydrocarbons include ethers, esters, ketones, acidsand alcohols. In specific the one or more cracked products may containphenols.

Fractionation may be carried out in any manner known to the skilledperson in the art to be suitable for fractionation of products from acatalytic cracking unit. For example the fractionation may be carriedout as described in the Handbook titled “Fluid Catalytic Crackingtechnology and operations”, by Joseph W. Wilson, published by PennWellPublishing Company (1997), chapter 8, especially pages 223 to 235,herein incorporated by reference.

In a further embodiment at least one of the one or more productfractions obtained by fractionation are subsequently hydrodeoxygenatedto produce a hydrodeoxygenated product fraction. This/thesehydrodeoxygenated product fraction(s) may be used as biofuel and/orbiochemical component(s).

The one or more product fractions may contain one or moreoxygen-containing-hydrocarbons. Examples of suchoxygen-containing-hydrocarbons include ethers, esters, ketones, acidsand alcohols. In specific one or more product fractions may containphenols and/or substituted phenols.

By hydrodeoxygenation is herein understood reducing the concentration ofoxygen-containing hydrocarbons in one or more product fraction(s)containing oxygen-containing hydrocarbons by contacting the one or moreproduct fraction(s) with hydrogen in the presence of ahydrodeoxygenation catalyst. Oxygen-containing hydrocarbons that can beremoved include acids, ethers, esters, ketones, aldehydes, alcohols(such as phenols) and other oxygen-containing compounds.

The hydrodeoxygenation preferably comprises contacting of the one ormore product fractions with hydrogen in the presence of anhydrodeoxygenation catalyst at a temperature in the range from equal toor more than 200° C., preferably equal to or more than 250° C., to equalto or less than 450° C., preferably equal to or less than 400° C.; at atotal pressure in the range of equal to or more than 10 bar absolute toequal to or less than 350 bar absolute (1.0 to 35 MegaPascal); and at apartial hydrogen pressure in the range of equal to or more than 2 barabsolute to equal to or less than 350 bar absolute (0.2 to 35MegaPascal).

The hydrodeoxygenation catalyst can be any type of hydrodeoxygenationcatalyst known by the person skilled in the art to be suitable for thispurpose.

The hydrodeoxygenation catalyst preferably comprises one or morehydrodeoxygenation metal(s), preferably supported on a catalyst support.The catalyst support is preferably inert as a hydrodeoxygenationcatalyst at the hydrodeoxygenation conditions.

The one or more hydrodeoxygenation metal(s) are preferably chosen fromGroup VIII and/or Group VIB of the Periodic Table of Elements. Thehydrodeoxygenation metal may for example be present as a mixture, alloyor organometallic compound.

Preferably the one or more hydrodeoxygenation metal(s) is chosen fromthe group consisting of Nickel (Ni), Chromium (Cr), Molybdenum (Mo),Tungsten (W), Cobalt (Co), Platinum (Pt), Palladium (Pd), Rhodium (Rh),Ruthenium (Ru), Iridium (Ir), Osmium (Os), Copper (Cu), Iron (Fe), Zinc(Zn), Gallium (Ga), Indium (In), Vanadium (V) and mixtures thereof. Theone or more metal(s) may be present in elementary form; in the form ofalloys or mixtures; and/or in the form of oxides, sulfides or othermetal-organic compounds.

If the hydrodeoxygenation catalyst comprises a catalyst support, thecatalyst support may comprise a refractory oxide or mixtures thereof,preferably alumina, amorphous silica-alumina, titania, silica, ceria,zirconia; or it may comprise an inert component such as carbon orsilicon carbide. The catalyst support may further comprise a zeoliticcompound such as for example zeolite Y, zeolite beta, ZSM-5, ZSM-12,ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-41, and ferrierite.

Most preferred are hydrodeoxygenation catalysts comprising Rhodium onalumina(Rh/Al₂O₃), Rhodium-Cobalt on alumina (RhCo/Al₂O₃), Nickel-Copperon alumina(NiCu/Al₂O₃), Nickel-Tungsten on alumina (NiW/Al₂O₃),Cobalt-Molybdenum on alumina(CoMo/Al₂O₃) or Nickel-Molybdenum on alumina(NiMo/Al₂O₃).

If the one or more product fractions also contain one or moresulphur-containing hydrocarbons it may be advantageous to use asulphided hydrodeoxygenation catalyst. If the hydrodeoxygenationcatalyst is sulphided the catalyst may be sulphided in-situ or ex-situ.Such in-situ or ex-situ sulphiding can be carried out in any mannerknown by the skilled person to be suitable for in-situ or ex-situsulphiding. In the case of in-situ sulphiding, a sulfur source, usuallyhydrogen sulphide or a hydrogen sulphide precursor, is preferablysupplied to the hydrodeoxygenation catalyst before operation of theprocess in a hydrodeoxygenation reactor. In addition it may beadvantageous to add a small amount of hydrogen sulphide during operationof the hydrodeoxygenation process to keep the catalyst sufficientlysulphided.

In addition to the hydrodeoxygenation, the one or more product fractionsmay be subjected to hydrodesulphurization, hydrodenitrogenation,hydrocracking and/or hydroisomerization. Hydrodesulphurization mayreduce the concentration of any sulphur-containing hydrocarbons.Hydrodenitrogenation may reduce the concentration of anynitrogen-containing hydrocarbons. Hydroisomerization may increase theconcentration of branched hydrocarbons. Hydrocracking may further crackthe product in smaller compounds.

Such hydrodesulphurization, hydrodenitrogenation, hydrocracking and/orhydroisomerization may be carried out before, after and/orsimultaneously with the hydrodeoxygenation.

In a preferred embodiment the one or more hydrodeoxygenated product(s)produced in the hydrodeoxygenation can be blended with one or more othercomponents to produce a biofuel and/or a biochemical. Examples of one ormore other components with which the one or more hydrodeoxygenatedproduct(s) may be blended include anti-oxidants, corrosion inhibitors,ashless detergents, dehazers, dyes, lubricity improvers and/or mineralfuel components.

Alternatively the one or more hydrodeoxygenated product(s) can be usedin the preparation of a biofuel component and/or a biochemicalcomponent. In such a case the biofuel component and/or biochemicalcomponent prepared from the one or more hydrodeoxygenated product may besubsequently blended with one or more other components (as listed above)to prepare a biofuel and/or a biochemical.

By a biofuel respectively a biochemical is herein understood a fuel or achemical that is at least party derived from a renewable energy source.

What is claimed is:
 1. A process for regenerating a coked catalyticcracking catalyst, comprising contacting the coked catalytic crackingcatalyst with an oxygen containing gas at a temperature of equal to ormore than 550° C. in a regenerator to produce a regenerated catalyticcracking catalyst, heat and carbon dioxide, wherein the coked catalyticcracking catalyst comprises carbon-containing deposits, whichcarbon-containing deposits comprise 1 wt% to 25 wt% bio-carbon, based onthe total weight of carbon present in the carbon-containing deposits,wherein the coked catalytic cracking catalyst is produced by contactinga solid biomass material with a catalytic cracking catalyst at atemperature of more than 400° C. in a catalytic cracking reactor.
 2. Theprocess of claim 1 wherein the oxygen- containing gas comprises morethan 21 vol. % oxygen, based on the total volume of theoxygen-containing gas.
 3. The process of claim 1 wherein the cokedcatalytic cracking catalyst is produced by contacting the biomassmaterial and a fluid hydrocarbon feed with a catalytic cracking catalystat a temperature of equal to or more than 400° C. in a catalyticcracking reactor, wherein the catalytic cracking reactor is a riserreactor and the biomass material is supplied to the riser reactorupstream of the fluid hydrocarbon feed.
 4. The process of claim 3wherein the biomass material is a solid biomass material.
 5. The processof claim 1 wherein the coked catalytic cracking catalyst is contactedwith the oxygen containing gas in the regenerator at a temperature ofequal to or more than 700° C.
 6. The process of claim 1 wherein part ofthe produced heat is subsequently used to heat water and/or generatepressurized steam.